Polysiloxane esters of hydrogenated bisphenol a



United States Patent 3,055,864 POLYSILOXANE ESTERS 0F HYDROGENATED BISPHENOL A Paul M. Kerschner, Merccrville, NJ., and Albert I. Meyers, New Orleans, La., nssignors to Cities Service Research and Development Company, New York, N.Y., a corporation of New Jersey No Drawing. Filed Feb. 26, 1960, Ser. No. 11,152 13 Claims. (Cl. 260--46.5)

[0 0 :l o 0 RO- llallon'o allon wherein n is an integer from 1 to 4, R is a monovalent aliphatic hydrocarbon radical having from 3 to 18 carbon atoms; A is the divalent radical R! R --(cHa),Sllos 1- (cm),

i l at wherein R" and R'" are alike or different and are selected from the group consisting of alkyl radical having from 1 to 12 carbon atoms, aryl, alkylaryl and aralkyl, y has a value from 2 to 5, n is an integer from 1 to 8; and R is the divalent radical CHr-OH] CHrCHl Q a -O OHMC CH OHr-C a CH C 1 wherein M is selected from the group consisting of a)ra) r- 2 and C H In the foregoing structure R represents the residue of a monoalcohol having from 3 to 18 carbon atoms which may be in a straight, branched or cyclic configuration. Preferably the alcohol used will be of the aliphatic type and can be selected from the following alcohols which have been found suitable for preparing these new polyesters: propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, Z-ethylbutyl, 2-ethylhexyl, heptyl, octyl, the C oxo alcohols, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

As previously defined in the foregoing formula, A represents the divalent radical obtained from the polysiloxane dibasic acid. These acids are known to those skilled in the art and may be prepared by subjecting a chlorinated alkyl disiloxane to the malonic ester synthesis followed by hydrolysis and decarboxylation. The siloxane grouping appearing in the brackets in the divalent acid residue radical may be increased by treating a disiloxane ester with concentrated sulfuric acid in the presence of octamethylcyclotetrasiloxane. panding the siloxane center of the dibasic acid is more specifically described in JACS 75, 6337 (1953). The R" and R'" substituents in the polysiloxane grouping can be varied and may include alkyl radicals having not more This method of ex- 3,055,864 Patented Sept. 25, 1962 than 12 carbon atoms, aryl, alkylaryl having not more than 12 carbon atoms and aralkyl having not more than 12 carbon atoms. These substituents may be alike or dilferent from the substituents on the silane radical. As previously defined n has a value of from 1 to 8 which value is determined by treating the desired disilox'ane ester compound as described above. When polyesters of this invention are being prepared for use as synthetic lubricants it is preferred that the upper limit values for n and the carbon content of the substituents represented by R and R' not be exceeded since final polyester structures prepared with groupings exceeding the stated limits will have molecular weights and viscosities unsuitable for lubricant purposes. With respect to the dibasic acid preparation a more complete description will be found in JACS 78, 2010 (1956).

The divalent radical of the foregoing structure identified as R is the residue of the selected hydrogenated bisphenol A. Hydrogenated bisphenols suitable for the purpose of the present invention include 2,2(bis-4-hydroxycyclohexyl) propane, 1,2(bis-4-hydroxycyclohexyl) propane, 1,1(bis-4-hydroxycyclohexyl) propane and 1,3- (bis-4-hydroxycyclohexyl) propane. The structure of the divalent residue of the bisphenol represented by R' has the following structurein which M is selected from the group consisting of For convenience in the specification and in the claims hereafter, the residue identified by R will be written as DMD in which D represents the saturated cyclohexyl ring OKs-CH:

To prepare the new compounds of the present invention the dicarboxylic acid selected is reacted with the selected hydrogenated bisphenol in a molar ratio of acid to diol of 1.25:1 to 2:1 under esterification conditions with water being removed to form a polyester product. Limitation or chain termination of the polyester is accomplished by esterifying the intermediate product of the diacid-diol reaction with a monoalcohol which is added in at least a stoichiometric quantity or in slight excess of from 5 to 10% to insure complete chain termintation.

The esterification reaction is generally carried out by refluxing the reactants in a flask or vessel equipped with a reflux condenser and a water-trap. The latter provides a means for removing water of esterification from the reaction zone. The removal of water is accomplished by using an azeotrope forming solvent such as toluene, benzene, xylene, or the like. Depending on the quantities of reactants used, esterification can be completed in from 1 to 6 hours when reflux is carried out at a temperature of between about C. and C. Reflux temperature is determined by the'particular solvent used to form the azeotrope. An acid catalyst is used to improve the rate of esterification and suitable for this purpose are sulfuric acid, phosphoric acid, p-toluene sulfonic acid, hydrogen chloride, thionyl chloride, acetyl chloride, boron trifluoride, and trifluoroacetic acid.

In carrying out the reaction the diacid and diol are first esterified in the presence of the azeotrope forming solvent and a catalytic amount of acid catalyst. Reflux is carried out until the theoretical amount of water of 3 esterification is recovered in the water trap. This amount EXAMPLE 2 of water would, of course, depend on the molar quantifies To 556 8m (02 mol) 4 4 6 640' M44 64mm:

of the reactants used. After recovery of the theoretical amount of water, a stoichiometric amount or slight excess of the monoalcohol is added to the reaction mixture and reflux is again carried out until a further theoretical amount of water is recovered. After esterification with the chain terminating monoalcohol is complete the reaction mixture is cooled, washed with water, washed with a 10% sodium carbonate solution, and again washed with 10 water to remove any free acid present. The solvent and excess alcohol are then distilled from the reaction mixture at a reduced pressure.

The examples which follow will more clearly de- 5-oxanonanedioic acid, 24.0 gm. (0.1 mol) 1,1-(bis-4- hydroxycyclohexyl) propane are added, using the apparatus described in Example 1. Toluene (250 ml.) and 1 gm. p-toluene sulfonic acid catalyst are added to the system and esterification is carried out according to the method described in Example 1. After esterification is essentially complete as indicated by recovering the theoretical amount of water, 20.0 gm. (0.2 mol) of cyclohexanol is added. Refluxing is again carried on until esterification is complete. The product, recovered in the manner described in Example 1, is of the following f l senbsrctliie manner m which these new polyesters may be 0mm CH om O OHPOH, mm P ep I EXAMPLE 1 [OIHIIO CH|CH| l0AiCHtCH| 0O C-H Into a 100 ml., three neck, round-bottom flask provided with a mechanical stirrer, a reflux condenser fitted EXAMPLE 3 with a water trap, and a thermometer, 55.6 gm. (0.2 To 8m. mol) 4,466,8,8 hememy1 4,6,8 9 sf q fl1 trisila-S,7-dioxaundecanedioic acid, 24.0 gm. 0.1 mol) acid are added. To this acid 24.0 gm. (0.1 mol) of ZMbiMhYdroxYcwlohexYl) propane is added using 2, 2(b1s-4-hydroxycycl0hexyl) PIPP P are added along the apparatus described in Example 1. Toluene (250 nh 1 f 34 111 sulfa me acid catalyst an 250 1.) and 1 gm. p-toluene sulfonic acid catalyst are added of mlucne- T mature aglmmd W and to the system and esterification is carried out according the tempuam" lncrmdby F fi hmtmg to the method described in Example 1. After esterificafluxing begins. The reaction is continued at the reflux tion is essentially complete as indicatcd by recovering mmpfl'amrf approxlmatdlfi of the theoretical amount of water, 26.0 gm. (0.2 mol) "col/end I{ uually 4 to 6 of 2-ethylhexanol is added. Refluxing is again carried hours. After esterification is essentially complete, 19.5 on um t ifi ti is common The product i 8 of ll'amyl 81601101 added flask covered in the manner described in Example 1 and is of and refluxing is again brought about by external heating. h for ula of on. on. o tam-0H, on, [OHKOHMCIUCHD UHaO OHsOH|Ai OAl 1 03101118 0-04! OH An tedadgllifitglflll 3.: of water are erleegveredih U-nre- 40 EXAMPLE4 ac co 0 an sovent are remov rom e reaction system by distillation at atmospheric pressure. The a gal? F236 j'lig giz f crude ester product remaining, after solvent and alcohol 016 acid, 24 (OJ mol) l,l (bis 4 hydmxycyclo removal: 15 washed wlth 10% sodmm Embonate, hexyl) propane is added, using the apparatus described and again with water to remove unreacted acids. The in Example 1, Toluene (250 ml.) and 1 gm. p-toluene final Product is by distillafiml at a P sulfonic acid catalyst are added to the system and esteriof about 0.5 to 1.0 mm. Hg. The recovered product fication is carried out according to the method described is of the following formula in Example 1. After esterification is essentially complete as indicated by recovering the theoretical amount 0 1 of water, 26.0 gm. 0.2 mol) 2-ethylhexanol is added. OlHuOECH|OHsAl-O-SlOH|OH|EO-C EC (5 Refluxing is again carried on until esterification is comm Q, 1, plete. The product is recovered in the manner described in Example 1 and is of the formula 0 OH; OKs-OH: sHI OH;(CH OH(Os 03108015011141 The product has the following chemical and physical as EXAMPLE 5 characteristics.

Sap. N 7 Following the method of the previous example 55.6

Sr, per 333 gm. (0.2 mol) 4,4,6,6-tetramethyl-4,6-disila-5-oxanonane- V1s., F 4679 dioic acid are reacted with 31.9 gm. (0.13 mole)l,2- (bis-4-hydroxycyclohexyl) propane in the presence of v.1 1395 approximately 250 ml. toluene and 1 gm. p-toluene sul- Pour pt" F fonic acid. After reflux yields 4.9 gm. of water, 13.7

Flash pt" 0 F 505 gms. (0.134 mol) 2-ethylbutanol is added and reflux Fire pt., -F 550 again carried out until esterification is complete. The

3,055,864 product is recovered in the manner described in the hydroxycyclohexyl) propane is added, using the ap previous examples and is of the formula paratus described in Example 1. Toluene (250 ml.)

EXAMPLE 6 and 1 gm. p-tgluene sulfonic acid catalyst are added to e system an esterification is carried out according to gg if gg g gg gffl ggfi ffi m the method described in Example 1. After esterification 2,2(bis 4 hydroxycyclohexyl) propane is added using is essentially complete as lndrcated by recovering the the apparatus described in Example 1. Toluene (250 theoretical amount of water, 26.0 gm. (0.2 mol) of 1 and 1; gm @{oluene ulfoni i catalyst are the mixed C oxo alcohols is added. Refiuxing is again dd d t th system d ifi ti i i d t carried on until esterification is complete. The product according to the method described in Example 1. After is recovered in the manner described in Example 1 and esterification is essentially complete as indicated by reis of the formula 0 CH; CH. 0 CHI-"CH! 0H, [CS HO CHIOHsAl-O-F-CHQOHt 0-C fio crnonr- H; H; CHz-C 11:

covering the theoretical amount of water, 34.0 gm. (0.26 EXAMPLE 9 mol) of 2-ethylhexanol is added. Refiuxing is again T n fi k carried on until esteritication is complete. The product 1, L u iz 2 1??? 43 56? it h ia ni th ijffi i recovered the descnbed.m Example 9 trisila-S,7-dioxaundecanedioic acid are added. To this has the followlng chemical and physical characteristics: acid 240 gm (OJ m 01) of 1,1 (bis 4 hydmxycyclo Sap. No 198 hexyl)propane are added along with 1 gm. of p-toluene Si, percent- 11.0 sulfonic acid catalyst and 250 cc. of toluene. The mix- Vi ture is agitated vigorously and the temperature increased 100 F 184.8 by external heating until refluxing begins. After esteri- 20,62 fication is essentially complete, 26.0 gm. (0.2 mdl) of V.I 124.0 C 0x0 alcohols are added to the flask and refluxing Pour pt., F 85 is again brought about by external heating. Unreacted Flash pt F 515 alcohol and solvent are removed from the reaction sys- Fire pt., F 570 tem by distillation at atmospheric pressure. The crude ester product is washed with water, 10% sodium car- EXAMPLE 7 bonate and again with water to remove unreacted acids.

To 70.4 gm. (0.2 mol) 4,4,6,6,8,8-hexamethyl-4,6,8- The final product is recovered by distillation at a prestrisila-S,7-dioxaundecanedioic acid, 24.0 gm. 1,3 (bis-4- sure of about 0.5 to 1.0 mm. Hg and is of the formula 0 OH. I- OH; 0 /OH|CH1 I 0.11. otmio omomsi 0-31 OHICHQ O-CH 0- H H; L Hs a CHrCfl: .Jt

hydroxycyclohexyl) propane is added, using the appa- EXAMPLE 10 rams described in Example.1' Toluene (250 and According to the procedures previously described, 100 1 Woluene 1 f catlyst gm. 0.2 mol) of 4,4,6,6,8,8,10,10,12,l2-decamethyl-4,6, System and esten ficau?n earned accordm? to 8,10,l2-pentasila-5,7,9,l1-tetraoxapentadecandioic acid the method descl'lbed P After estenfifia are reacted with 24.0 gm. (0.1 mol) of 2,2 (bis-4-hyis essentially comPlcte as mdlcated y recovering droxycyclohexyl) propane. After esterification is comthe theoretical am f Water, g 55 plete, 31.6 gm. (0.2 mol) of decanol are addedto the decanol is added. Refiuxing is again carried on until product. The final product is washed and recovered esterification is complete. The product is recovered in by distillation and is of the formula 0 (1H3 CH] '1 O CHI-CHI CH; [Ci H| O CH:CH1Sl-O l CHsCHr-lLO-Cfi C HgL (L1H: i CHPCfil L $11;

the manner described in Example 1 and is of the for- EXAMPLE 11 mula According to the procedures previously described, 55.6

0 on. on, o oar-0H, [CmH2|O CHgCHAl- O l CHgUHzPO-Cfi C-CHlCH:

(EH1 L (1H1 J1 \CHPOI J! EXAMPLE 8 gm. (0.2 mol) of 4;4,6,6-tetramethyl-4,6-disila-5-oxano- To 55.6 gm. (0.2 mol) 4,4,6,6-tetramethyl-4,6-disilananedioic acid are reacted with 2.4.0 gm. (0.1 mol) of S-oxanonanedioic acid, 24.0 gm. (0.1 mol) 1,2(bis-4- 1,2 (bis-4-hydroxycyclohexyl) propane. After the ester- 7 ification is complete, 31.6 gm. (0.2 mol) of decanol are added. The final product is recovered as described previously.

EXAMPLE 12 To a flask of the type described in Example 1, 55.6 gm. (0.2 mol) 4,4,6,6-tetramethyl-4,6-disila--oxanonanedioic acid are added. To this acid 31.9 gm. (0.133 mol) of 1,3 (bis4-hydroxycyclohexyl) propane are added along with 1 gm. of p-toluene sulfonic acid catalyst and 250 cc. of toluene. The mixture is agitated vigorously and the temperature increased by external heating until refluxing begins. The reaction is continued at the reflux temperature until esterification is complete. 17.4 gm. (0.134- mol) of 2-ethylhexanol are added to the reaction product and refluxing is resumed. The crude ester product is washed with water, sodium carbonate, and water. The final product is recovered by distillation at a pressure of about 0.5 to 1.0 mm. Hg.

EXAMPLE 13 According to the procedures described in Example 1,

70.4 gm. (0.2 mol) of 4,4,6,6,8,8-hexamethyl-4,6,8-trisila- 5,7-dioxaundecanedioic acid are reacted with 31.9 gm. (0.133 mol) of 1,2 (bis-4-hydroxycyclohexyl) propane. Upon completion of the esterification reaction, 19.2 gm. (0.133 mol) nonanol are added. The final product is recovered as described.

EXAMPLE 14 According to the procedures of Example 1, 61.2 gm. (0.2 mol of 5,5,7,7-tetramethyl-5.7 disila-6-oxaundecandioic acid are reacted with 24.0 gm. (0.1 mol) of 2,2 (bis-4-hydroxycyclohexyl) propane. Upon completion of the esterification reaction, 26.0 gm. (0.2 mol) plete, 0.2 mol of heptanol are added. The final product recovered as described.

EXAMPLE l5 5 According to the procedures described, 0.2 mol of 7,7,9,9-tetramethyl-7,9-disila 8 oxapentadecandioic acid are reacted with 0.1 mol of 2,2 (bis-4-hydroxycyclohexyl) propane. After esterification is substantially complete, 0.2 mols of heptanol are added. The final product is recovered as described and is of the formula:

As has been previously indicated the new polyesters of the present invention when prepared according to the method described and within the structural limits defined by the general formula possess properties and characteristics making them particularly suitable for lubricating purposes as synthetic lubricants. The excellent lubricating properties of these new polyesters are shown in the data of the tables which follow in which the wear properties of the polyesters prepared according to Example 6 and Example 1 respectively were evaluated in the standard Shell 4 ball test. This test is based on the use of an apparatus that includes 3 rigidly held 16" metal balls (type 52-100 steel balls) submerged in the lubricant to be tested in a metal cup. A 4th ball of the same size and material is pressed into contact with the 3 fixed balls by an adjustable loading arm and allowed to rub over a fixed period of time. The contact points on the 3 stationary balls grow to circular scars as wear progresses. The average diameter of these scars in millimeters after the fixed period of operation at a particular speed and load is taken as a measure of wear.

The temperature at which the test is carried out may be varied from room temperature to as high as 170' C.

TIONAL ORGANOSILICON ESTERS WITH PETROLEUM OIL AND WITH COMMERCIAL A" SILICONE FLUID Bear diameter in mm.

' Sample No.

Exampleti neutral Silicone mineral oil Extreme Pressure-Wear Scar diameter in mm.

Sample No.

Silicone Sear diameter in mm.

pppp mu IO car o Sear diameter in mm.

Sample No.

In the foregoing table the neutral mineral oil is a standard base oil having an API gravity of 32 (min.); specific gravity (max.) 0.8654; flash, 00C, F. (min.) 380; fire, CCC, F. (min.) 430; viscositySUS at 100 P. 100-110; at 210 F. 40; V.I range (min.) 95, and pour point, F. (max.) 0. The silicone oil is a commercially available polymethyl siloxane oil manufactured by Dow Corning Company under the name 200 fluid. It will be noted that the polyester of the present invention possesses superior wear properties to that of either the conventional mineral or commercially available silicone oil both in the wear and extreme pressure tests. The excellent viscosity characteristics coupled with the molecular weights, flash, fire and pour point values for these polyesters make them particularly suitable for use as lubricants.

While this invention has been described with some degree of particularity with respect to the structures of the compounds used and the method by which these polyesters are prepared, it is to be understood that the only limitations on the scope of the invention to be applied are those imposed by the scope of the claims ap pended hereto.

We claim:

1. A new composition of matter, a polyester having the formula wherein n is an integer from 1 to 4, R is a monovalent aliphatic hydrocarbon radical having from 3 to 18 carbon atoms, A is the divalent radical RI! R" l i :)y1k1-[0i: J (CH1),- wherein R" and R are selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl, radicals having not more than 12 carbon atoms, y has a value from 2 to 5, n has a value of from 1 to 8, and R is the divalent radical --DMD wherein D represents CHr-C:

and M is selected from the group consisting of --C(CH --CH(CH )CH --CH(C H and -C H 2. A new composition of matter as claimed in claim 1 wherein R is 'C5Hu A is -'(C a)z a)z 3)a( 2)2 R is DC(CH D-, and n is 1 3. A new composition of matter as claimed in claim 1 wherein R iS A i 2)2 a)2 a)2( 2)z- R is DC(OH D and n is 2 4. A new composition of matter is claimed in claim 1 wherein R is CH (CH CH(C H )CH A is (CH Si(CH OSi(CH OSi(CH ),(CH R is -DO(CH D and n is 1 5. A new composition of matter as claimed in claim 1 wherein R is A is 2): s)2 a 5)2 o c):

a)2( a)r- IR is -DCH(C H )D and n is 1 6. A new composition of matter as claimed in claim 1v wherein R iS A is z)2 s)a a)2( 2)r- R is DCH(CH )OH,D- and n is 2 7. A new composition of matter as claimed in claim 1 wherein 10 8. A new composition of matter as claimed in claim 1 wherein R is 1o 21 A is (CI-I Si(CH OSi(CH OSi(CH ),(CH R is -DC ,H D- and n is 1 9. A new composition of matter as claimed in claim 1 wherein R is CgH A is 2)2 s)2 a)2( s)2- R' is -DCH(CH )CH,D- and n is 1 10. A new composition of matter, a polyester having the formula r0 0 l 0 o R-0- ii-A- -0-R'0 -ii-Aiio1z wherein n is an integer from 1 to 4, R is a monovalent aliphatic hydrocarbon radical having from 3 to 18 carbon atoms, A is the divalent radical I I" OH: I -(oH, ,-si0-s1 0H,),-

lHs I. i .In' wherein y is an integer from 2 to 5, n is an integer from 1 to 8, and R' is the divalent radical --DMD wherein D represents R is id ai Y is 2 n is 4 R is DC(CH ),D n is l 13. A new composition of matter as claimed in claim 10 wherein R is 0 H A is s)s s)a s)a( z)s- R is DC(CH,) D n is 1 References Cited in the file of this patent UNITED STATES PATENTS Kerschner et al Dec. 8, 1,959

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noo 3,055,864 September 25, 1962 Paul M. Kerschner et al6 It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 24 for "follow" read following columns 5 and 6 ,lines 3 to 7, the formula should appear as shown below instead of as in the patent:

CH3 (I31 fi /on -cn ([314 ca cn cmc a )cH occH cH si-o-si-cH cH co-ca HC CH-CHQ CH3 (:5 I CH2CH2 2 column 7, line 37, for "plate, 0.2 mol of heptanol" read 7 of C8 oxo"alc oh o1s line 40, for "EXAMPLE l5 5" read EXAMPLE l5 column 10 lines 16 to 18-, the formula should appear vas shown below instead of as in the patent:

same column 10, line 35 for ",-CH H read -C H Signed and sealed this 26th day of February 1963-.

(SEAL) Attest:

ESTON G. JOHNSON DAVID L. LADD Attestin'g Officer Commissioner of Patents 

1. A NEW COMPOSITION OF MATER, A POLYESTER HAVING THE FORLULA 